Polyestrimethylene terephthalate polyester

ABSTRACT

A polyester based on poly(trimethylene terephthalate) consisting essentially of trimethylene terephthalate repeating units, comprising at least one kind of compound selected from the group consisting of alkali metal compounds, alkaline earth metal compounds and manganese compounds in an amount of 10 to 150 ppm expressed in terms of the metal element in a molar ratio of the total amount of elements of the contained alkali metal elements, alkaline earth metal elements and manganese element to the amount of the contained phosphorus element within the range of the following formula (I): 
     0≦P/M≦1  (I) 
     wherein, P is the molar amount of the phosphorus element in the polyester; M is the total amount of the alkali metal elements, alkaline earth metal elements and manganese element.

TECHNICAL FIELD

[0001] The present invention relates to a polyester. More particularly,the present invention relates to a polyester based on poly(trimetyleneterephthalate) slightly causing yellowing after light irradiation andhaving improved light resistance.

BACKGROUND ART

[0002] As well known, polyesters have been widely used as fibers,resins, films and the like due to excellent performances thereof.Especially, polyester fibers comprising polyethylene terephthalate andhaving excellent dimensional stability, heat, chemical and lightresistances and the like have been utilized in various fieldsirrespective of clothing and nonclothing uses.

[0003] In the situation, attention has recently been paid to polyesterfibers based on polytrimethylene terephthalate and a woven or a knittedfabric comprising the polyester fibers so as to exhibit hand anddyeability which are difficult to realize from the conventionalpolytrimethylene terephthalate [for example, JP-A (hereunder, JP-A means“Japanese Unexamined Patent Publication”) 11-200175]. The polyesterfibers based on the polytrimethylene terephthalate, however, haveproblems that degree of yellowing in light irradiation is greater thanthat of polyethylene terephthalate and light resistance is inferior tothat of the polyethylene terephthalate.

[0004] As a method for improving the whiteness of the polytrimethyleneterephthalate, the addition of a phosphorus compound duringpolymerization is proposed in, for example WO99/11709. An improvement inlight resistance, however, cannot be expected by the method though themelt stability is improved.

[0005] On the other hand, for example, JP-A 3-234812 describes a methodfor adding a manganese compound, an antimony compound and a germaniumcompound to polyethylene terephthalate as a method for improving thelight resistance of the polyester fibers. The method relates to theinhibition of the strength deterioration of the polyethyleneterephthalate fibers and is a technique different from the prevention ofyellowing, especially the prevention of yellowing of thepolytrimethylene terephthalate fibers.

[0006] U.S. Pat. No. 5,872,204 describes the use of a manganese compoundas a catalyst usable together with an antimony compound catalyst as atechnique for adding a manganese compound to the polytrimethyleneterephthalate. However, there is no description of an improvement inlight resistance by the method, which has problems that foreignmaterials are readily produced in spinnerets during fiber formationbecause the antimony compound is used.

DISCLOSURE OF THE INVENTION

[0007] It is an object of the present invention to eliminate theproblems possessed by the prior art and to provide a polyester based onthe polytrimethylene terephthalate slightly causing yellowing afterlight irradiation and having improved light resistance.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] The mode for carrying out the present invention will be detailedhereinafter.

[0009] The polyester based on the polytrimethylene terephthalate is apolyester consisting essentially of trimethylene terephthalate repeatingunits.

[0010] The expression “consisting essentially of trimethyleneterephthalate repeating units” refers to “the trimethylene terephthalaterepeating units account for 85 mole % or more, preferably 90 mole % ormore in the whole repeating units constituting the polyester.

[0011] It is necessary for the polyester of the present invention tocontain at least one kind of compound selected from the group consistingof alkali metal compounds, alkaline earth metal compounds and manganesecompounds in an amount of 10 to 150 ppm expressed in terms of the metalelement. When the content of the element is less than 10 ppm, the lightresistance of the finally obtained polyester fibers becomesinsufficient. On the other hand, when the content exceeds 150 ppm, it isundesirable that the yellowness of the polyester polymer per se isincreased and the yellowing and lowering of the molecular weight duringremelting are increased. The content of the element is preferably withinthe range of 150 to 120 ppm, especially preferably within the range of20 to 100 ppm.

[0012] Examples of the alkali metal used in the present inventioninclude lithium, sodium, potassium, rubidium and the like. Examples ofthe alkaline earth metal include magnesium, calcium, strontium and thelike.

[0013] Acetates, benzoates, hydrochlorides, formates, oxalates,nitrates, carbonates and the like can be used as the alkali metalcompounds, alkaline earth metal compounds and manganese compoundsemployed in the present invention. Acetates and benzoates are preferablefrom the viewpoint of solubility in the polyester polymer. Furthermore,the compounds may be hydrates or anhydrides.

[0014] Further, in the polyester of the present invention, it isnecessary that the molar ratio of the total amount of elements of thecontained alkali metal elements, alkaline earth metal elements andmanganese element to the amount of the contained phosphorus elementsatisfies the relationship of the following formula (I):

0≦P/M≦1  (I)

[0015] wherein, P is the molar amount of the phosphorus element in thepolyester; M is the total molar amount of the alkali metal elements,alkaline earth metal elements and manganese element.

[0016] In the formula (I), when P/M exceeds 1, the light resistance ofthe finally obtained fibers becomes insufficient. The P/M is preferablywithin the range of 0 to 0.8, especially preferably within the range of0 to 0.6.

[0017] It is preferable that the polyester of the present inventionsimultaneously satisfies the following respective requirements (a) to(d):

[0018] (a) the intrinsic viscosity is within the range of 0.5 to 1.6,

[0019] (b) the content of dipropylene glycol is within the range of 0.1to 2.0% by weight,

[0020] (c) the content of a cyclic dimer is within the range of 0.01 to5% by weight and

[0021] (d) the color b value after crystallization is within the rangeof −5 to 10.

[0022] For explanation of the respective requirements, the mechanicalstrength of the finally obtained fibers is sufficiently high andhandleability is more improved when the intrinsic viscosity is withinthe above range. The intrinsic viscosity is more preferably within therange of 0.55 to 1.5, especially preferably within the range of 0.6 to1.4.

[0023] When the content of the dipropylene glycol is within the aboverange, the heat resistance of the polyester and mechanical strength ofthe finally obtained fibers become sufficiently high. The content of thedipropylene glycol is more preferably within the range of 0.15 to 1.8%by weight, especially preferably within the range of 0.2 to 1.5% byweight.

[0024] When the content of the cyclic dimer is within the above range,the yarn manufacturing property of the polyester is good. The content ofthe cyclic dimer is more preferably within the range of 0.02 to 1.8% byweight, especially preferably within the range of 0.03 to 1.5% byweight.

[0025] In addition, when the color b value after the crystallization iswithin the above range, the appearance of the finally obtained productsis improved. The color b value is more preferably within the range of −4to 9, especially preferably within the range of −3 to 8.

[0026] The polyester based on the polytrimethylene terephthalate of thepresent invention may be copolymerized with a component other thanterephthalic acid component and trimethylene glycol component in anamount within the range without deteriorating characteristics of thepolyester based on the polytrimethylene terephthalate, preferably withinthe range of 10 mole % or less based on the whole dicarboxylic acidcomponent.

[0027] Examples of the copolymerization components include aromaticdicarboxylic acids such as isophthalic acid, orthophthalic acid,naphthalenedicarboxylic acid, diphenyldicarboxylic acid,diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid,benzophenonedicarboxylic acid, phenylindanedicarboxylic acid,5-sulfoxyisophthalic acid metal salts or 5-sulfoxyisophthalic acidphosphonium salts, aliphatic glycols such as ethylene glycol,tetramethylene glycol, pentamethylene glycol, hexamethylene glycol,octamethylene glycol, decamethylene glycol, neopentylene glycol,diethylene glycol, triethylene glycol, polyethylene glycol,polytetramethylene glycol or cyclohexanediol, alicyclic glycols such as1,4-cyclohexanedimethanol or 1,4-cyclohexanediol, aromatic glycols suchas o-xylylene glycol, m-xylylene glycol, p-xylylene glycol,1,4-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxyethoxy)benzene,4,4′-bis(2-hydroxyethoxy)biphenyl,4,4′-bis(2-hydroxyethoxyethoxy)biphenyl, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxyethoxyethoxy)phenyl]propane,1,3-bis(2-hydroxyethoxy)benzene, 1,3-bis(2-hydroxyethoxyethoxy)benzene,1,2-bis(2-hydroxyethoxy)benzene, 1,2-bis(2-hyroxyethoxyethoxy)benzene,4,4′-bis(2-hydroxyethoxy)diphenyl sulfone or4,4′-bis(2-hyroxyethoxyethoxy)diphenyl sulfone, diphenols such ashydroquinone, 2,2-bis(4-hydroyphenyl)propane, resorcinol, catechol,dihydroxynaphthalene, dihydroxybiphenyl or dihydroxydiphenyl sulfone.One kind of the copolymerization components may be used alone or two ormore kinds may be used in combination.

[0028] The polyester based on the poly(trimethylene terephthalate) canbe produced by a conventionally known method. Namely, atransesterification method for subjecting a lower alkyl ester componentof terephthalic acid and a triniethylene glycol component totransesterification in the presence of a transesterification catalyst,providing a bisglycol ester and/or its percondensate and then carryingout polymerizing reaction in the presence of a polymerizing reactioncatalyst or a direct polymerization method or the like for directlyesterifying terephthalic acid with trimethylene glycol, producing anoligomer of a low degree of polymerization and subsequently carrying outthe polymerizing reaction in the presence of the polymerizing reactioncatalyst can be adopted.

[0029] The solid-phase polymerization for the purpose of increasing themolecular weight, reducing the content of terminal carboxyl groups andthe like can preferably be carried out by a conventional known method.

[0030] In the present invention, examples of compounds used as thetransesterification catalyst include manganese compounds, cobaltcompounds, calcium compounds, titanium compounds, sodium compounds,potassium compounds, zinc compounds, magnesium compounds and the like.The compounds may be used alone or two or more kinds may be used incombination. The titanium compounds used as a polycondensation catalystcan previously be added before transesterification and used as both thetransesterification catalyst and the polycondensation reaction catalyst.

[0031] Examples of preferably used titanium compounds employed as thepolymerizing reaction catalyst include a titanium tetraalkoxide alone, areaction product of at least one kind of compound selected from thegroup consisting of phthalic acid, trimellitic acid, hemimellitic acidand pyromellitic acid or anhydrides thereof with the titaniumtetraalkoxide, a reaction product of the titanium tetraalkoxide with aphosphonic acid compound, a reaction product of the titaniumtetraalkoxide with a phosphinic acid compound, a reaction product of thetitanium tetraalkoxide with a phosphate compound and a compound preparedby further carrying out reaction of the reaction product between atleast the one kind of compound selected from the group consisting ofphthalic acid, trimellitic acid, hemimellitic acid and pyromellitic acidor anhydrides thereof and the titanium tetraalkoxide with the phosphonicacid compound, phosphinic acid compound or phosphate compound. Titaniumtetrabutoxide is especially preferably used as the titaniumtetraalkoxide.

[0032] The molar ratio of the titanium tetraalkoxide to the phthalicacid, trimellitic acid, hemimellitic acid and pyromellitic acid oranhydrides thereof, phosphonic acid compound, phosphinic acid compoundand phosphate compound is especially preferably about 1.5 to 2.5 basedon the titanium tetraalkoxide.

[0033] Examples of the phosphonic acid compound to be reacted with thetitanium tetraalkoxide include phenylphosphonic acid, methylposphonicacid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonicacid, butylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid,biphenylphosphonic acid, naphthylphosphonic acid, anthrylphosphonicacid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid,4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid,2,4-dicarboxyphenylphosphonic acid, 2,5-dicarboxyphenylphosphonic acid,2,6-dicarboxyphenylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid,3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenylphosphonicacid, 2,3,5-tricarboxyphenylphosphonic acid,2,3,6-tricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonicacid, 2,4,6-tricarboxyphenylphosphonic acid and the like.

[0034] Examples of the phosphinic acid compound include phenylphosphinicacid, methylphosphinic acid, ethylphosphinic acid, propylphosphinicacid, isopropylphosphinic acid, butylphosphinic acid, tolylphosphinicacid, xylylphosphinic acid, biphenylylphosphinic acid,diphenylphosphinic acid, dimethylphosphinic acid, diethylphosphinicacid, dipropylphosphinic acid, diisopropylphosphinic acid,dibutylphosphinic acid, ditolylphosphinic acid, dixylylphosphinic acid,dibiphenylylphosphinic acid, naphthylphosphinic acid, anthrylphosphinicacid, 2-carboxyphenylphosphinic acid, 3-carboxyphenylphosphinic acid,4-carboxyphenylphosphinic acid, 2,3-dicarboxyphenylphosphinic acid,2,4-dicarboxyphenylphosphinic acid, 2,5-dicarboxyphenylphosphinic acid,2,6-dicarboxyphenylphosphinic acid, 3,4-dicarboxyphenylphosphinic acid,3,5-dicarboxyphenylphosphinic acid, 2,3,4-tricarboxyphenylphosphinicacid, 2,3,5-tricarboxyphenylphosphinic acid,2,3,6-tricarboxyphenylphosphinic acid, 2,4,5-tricarboxyphenylphosphinicacid, 2,4,6-tricarboxyphenylphosphinic acid,bis(2-carboxyphenyl)phosphinic acid, bis(3-carboxyphenyl)phosphinicacid, bis(4-carboxyphenyl)phosphinic acid,bis(2,3-dicarboxyphenyl)phosphinic acid,bis(2,4-dicarboxyphenyl)phosphinic acid,bis(2,5-dicarboxyphenyl)phosphinic acid,bis(2,6-dicarboxyphenyl)phosphinic acid,bis(3,4-dicarboxyphenyl)phosphinic acid,bis(3,5-dicarboxyphenyl)phosphinic acid,bis(2,3,4-tricarboxyphenyl)phosphinic acid,bis(2,3,5-tricarboxyphenyl)phosphinic acid,bis(2,3,6-tricarboxyphenyl)phosphinic acid,bis(2,4,5-tricarboxyphenyl)phosphinic acid,bis(2,4,6-tricarboxyphenyl)phosphinic acid and the like.

[0035] Furthermore, examples of the phosphate compound include monoalkylphosphates and monaryl phosphates such as monomethyl phosphate,monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate,monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate,monononyl phosphate, monodecyl phosphate, monododecyl phosphate,monolauryl phosphate, monooleyl phosphate, monotetradecyl phosphate,monophenyl phosphate, monobenzyl phosphate, mono(4-dodecyl)phenylphosphate, mono(4-methylphenyl) phosphate, mono(4-ethylphenyl)phosphate, mono(4-propylphenyl) phosphate, mono(4-dodecylphenyl)phosphate, monotolyl phosphate, monoxylyl phosphate, monobiphenylphosphate, mononaphthyl phosphate, monoanthryl phosphate and the like.

[0036] The polyester based on the poly(trimethylene terephthalate) ofthe present invention, if necessary, may contain a small amount of anadditive, for example, a lubricant, a pigment, a dye, an antioxidant, asolid-phase polymerization accelerator, a fluorescent brightener, anantistatic agent, an antimicrobial agent, an ultraviolet light absorber,a light stabilizer, a heat stabilizer, a light screen, a delusteringagent and the like.

[0037] In the polyester of the present invention, at least one kind ofcompound selected from the group consisting of alkali metal compoundsalkaline earth metal compounds and manganese compounds is contained at ahigh concentration exceeding 150 ppm to 10000 ppm expressed in terms ofthe metal element to provide a polyester containing the metal compoundat the high concentration. With a polyester based on thepoly(trimethylene terephthalate), is melt kneaded 0.5 to 50% by weightof the polyester containing the metal compound at the highconcentration. Thereby, at least the one kind of compound selected fromthe group consisting of the alkali metal compounds, the alkaline earthmetal compounds and the manganese compounds may be contained so as toprovide at least the one compound in an amount of 10 to 150 ppmexpressed in terms of the metal element in the polyester based on thepoly(trimethylene terephthalate).

[0038] In this case, when the amount of the polyester containing themetal compound at the high concentration is 0.5% by weight or less, itis difficult to uniformly disperse the metal compound in the polyester.When the amount exceeds 50% by weight, the production efficiency of thepolyester based on the poly(trimethylene terephthalate) is inferiorbecause the amount used of the polyester containing the metal compoundat the high concentration is too large. When the polyester containingthe metal compound at the high concentration is used, the amount thereofused is preferably within the range of 0.7 to 40% by weight, morepreferably within the range of 1 to 30% by weight.

[0039] When the polyester containing the metal compound at the highconcentration is to be used, the necessity for using a large amount ofthe polyester containing the metal compound at the high concentrationarises in order to maintain the light resistance of the finally obtainedfibers at a sufficient level if the content of the metal element is 150ppm or less. On the other hand, when the content of the metal elementexceeds 10000 ppm, it is difficult to control the quality of the finallyobtained fibers because the yellowness of the polyester containing themetal compound at the high concentration per se is increased and furtherthe lowering of molecular weight by thermal decomposition is marked ifthe content exceeds 10000 ppm. Thereby, the content of the metal elementis more preferably within the range of 300 to 8000 ppm, especiallypreferably within the range of 500 to 5000 ppm.

[0040] Methods for melt kneading the polyester containing the metalcompound at the high concentration with the polyester based on thepoly(trimethylene terephthalate) are not especially limited; however,examples of the methods include a method for adding a solid or a moltenpolyester containing the metal compound at the high concentration to thepolyester based on the poly(trimethylene terephthalate) melted with, forexample a twin-screw extruder using a side feeder or the like, a methodfor chip blending the polyester based on the poly(trimethyleneterephthalate) with the polyester containing the metal compound at thehigh concentration and then melt kneading the blended chips, a methodfor adding chips of the polyester containing the metal compound at thehigh concentration into a polymerizing reaction vessel in a polymerizingreaction stage of the polyester based on the poly(trimethyleneterephthalate polymerized by a batch method and the like.

[0041] The fibers comprising the polyester based on thepoly(trimethylene terephthalate) of the present invention may beproduced by melt spinning the polyester based on the poly(trimethyleneterephthalate) at a temperature within the range of 238 to 275° C., andyarn breakage during the spinning does not occur when the melt spinningtemperature is within the range. The melt spinning temperature ispreferably within the range of 239 to 270° C., especially preferablywithin the range of 240 to 265° C. The spinning speed when the meltspinning is carried out may be set within the range of 400 to 5000m/min. When the spinning speed is within the range, the strength of theobtained fibers is sufficient and the fibers can stably be wound. Thespinning speed is more preferably within the range of 500 to 4700 m/min,especially preferably within the range of 600 to 4500 m/min.

[0042] The shape of a spinneret used during the spinning is notespecially limited, and any of a circular, a modified cross-section, asolid, a hollow shapes and the like can be adopted.

[0043] A polyester dawn yarn based on the poly(trimethyleneterephthalate) in the present invention can be obtained by winding thepolyester fibers of the poly(trimethylene terephthalate) or, withoutwinding the polyester fibers once, and continuously subjecting thefibers to the drawing treatment.

[0044] The polyester fibers and polyester drawn yarn based on thepoly(trimethylene terephthalate) of the present invention have anintrinsic viscosity preferably within the range of 0.5 to 1.5. When theintrinsic viscosity is within the range, the mechanical strength of thefinally obtained fibers is sufficiently high and handling is improved.The intrinsic viscosity is more preferably within the range of 0.52 to1.4, especially preferably within the range of 0.55 to 1.3.

[0045] A fabric having a value of an increase in color b value of 2 orless after irradiation at a humidity of 50% RH and 60° C. for 80 hourswith a sunshine weatherometer can be obtained by using the polyesterfibers and/or polyester undrawn yarn of the present invention.

EXAMPLES

[0046] The present invention will be explained more specificallyhereafter with examples. The present invention, however, is not limitedby the examples at all. Respective values in the examples were measuredaccording to the following methods.

[0047] (1) Intrinsic Viscosity:

[0048] The intrinsic viscosity was obtained by carrying out measurementsat 35° C. according to a conventional method using o-chlorophenol as asolvent.

[0049] (2) Measurements of Calcium Content, Rubidium Content, ManganeseContent, Cobalt Content and Phosphorus Content in Polyester:

[0050] A sample polymer was thermally melted to prepare a circular disk,and the contents were obtained according to a conventional method usinga fluorescent X-ray apparatus manufactured by Rigaku Corporation.

[0051] (3) Measurements of Sodium Content, Potassium Content, LithiumContent and Magnesium Content in Polyester:

[0052] One g of a sample polymer was dissolved in 10 ml ofo-chlorophenol, mixed with 20 ml of 0.5 N-HCl and allowed to standovernight. The contents were obtained by carrying out measurements ofthe supernatant HCl solution according to a conventional method usingZ-6100 Polarized Zeeman Atomic Absorption Spectrophotometer manufacturedby Hitachi, Ltd.

[0053] (4) Content of Dipropylene Glycol

[0054] A sample polymer, together with an excessive amount of methanol,was sealed in a tube and subjected to methanolysis under conditions of260° C. for 4 hours in an autoclave, and the amount of dipropyleneglycol in the decomposition product was determined according to aconventional method using a gas chromatography (HP6890 Series GC Systemmanufactured by Hewlett-Packard Company). The weight percentage of thedipropylene glycol based on the weight of the measured polymer wasobtained.

[0055] (5) Content of Cyclic Dimer

[0056] In 1 ml of hexafluoroisopropanol, was dissolved 1 mg of a samplepolymer. A sample solution prepared by diluting the resulting solutionwith chloroform until the volume reached 10 ml was injected by using anapparatus in which two GPC columns TSK gel G2000H8 manufactured byWaters Corporation were connected in a model 486 liquid chromatographmanufactured by Waters Corporation. Chloroform was used as a developingsolvent, and the content of the cyclic dimer of the polymer was obtainedfrom a calibration curve of the previously prepared standard cyclicdimer.

[0057] (6) Color b Value After Crystallization

[0058] The color of chips was obtained after drying at 130° C. for 2hours and the color of fibers was obtained after knitting the fibersinto a knitted fabric according to a conventional method using acolor-difference meter (model: CR-200) manufactured by Minolta Co., Ltd.

[0059] (7) Tensile Strength and Tensile Elongation

[0060] Measurements were carried out according to the method describedin JIS L1070.

[0061] (8) Evaluation of Light Resistance

[0062] A sample prepared by knitting fibers into a knitted fabric wasirradiated under conditions of 60° C., 80 hours and a humidity of 50% RHwithout rainfall using a sunshine weatherometer (manufactured by SugaTest Instruments Co., Ltd.). The color b values of the sample before andafter the irradiation were measured to calculate an increase in color bvalue.

Reference Example 1 Production of a Catalyst Comprising a ReactionProduct of Titanium Tetrabutoxide with Trimellitic Anhydride

[0063] Tetrabutoxytitnium in an amount of 0.5 mole based on 1 mole oftrimellitic anhydride was added to a trimethylene glycol solution (0.2%)of trimellitic anhydride, and the resulting mixture was kept at 80° C.under atmospheric pressure in air and reacted for 60 minutes. Theresultant reaction mixture was then cooled to normal temperature, andthe produced catalyst was recrystallized with acetone in an amount of 10times. The deposited substance was filtered through a filter paper anddried at 100° C. for 2 hours to provide the objective catalyst.

Reference Example 2 Production of a Catalyst Comprising a ReactionProduct of Titanium Tetrabutoxide with Phenylphosphonic Acid

[0064] Tetrabutoxytitanium in an amount of 0.5 mole based on 1 mole ofphenylphosphonic acid was added to a trimethylene glycol solution (0.2%)of the phenylphosphonic acid, and the resulting mixture was kept at 120°C. under atmospheric pressure in air and reacted for 60 minutes toafford the objective catalyst as a white slurry.

Reference Example 3 Production of a Catalyst Comprising a ReactionProduct of Titanium Tetrabutoxide with Phenylphosphinic Acid

[0065] Tetrabutoxytitanium in an amount of 0.5 mole based on 1 mole ofphenylphosphinic acid was added to a trimethylene glycol solution (0.2%)of the phenylphosphinic acid, and the resulting mixture was kept at 120°C. under atmospheric pressure in air and reacted for 60 minutes toprovide the objective catalyst as a white slurry.

Example 1

[0066] A reactor equipped with a stirrer, a rectifying column and amethanol distilling off condenser was charged with 100 parts by weightof dimethyl terephthalate, 70.5 parts by weight of trimethylene glycoland 0.0316 part by weight of manganese acetate tetrahydrate as atransesterification catalyst, and transesterification was carried outwhile slowly heating up the mixture from 140° C. and distilling offmethanol produced as a result of the reaction to the outside of thesystem. The internal temperature reached 210° C. after the passage of 3hours from the start of reaction.

[0067] To the resulting reaction product, was added 0.0526 part byweight of titanium tetrabutoxide as a polymerizing reaction catalyst.The resulting mixture was then transferred to another reactor equippedwith a stirrer and a glycol distilling off condenser, and polymerizingreaction was carried out while slowly heating up the mixture from 210°C. to 265° C. and reducing the pressure from atmospheric pressure to ahigh vacuum of 70 Pa. The polymerizing reaction was finished when theintrinsic viscosity reached 0.75 while tracing the melt viscosity of thereaction system.

[0068] The molten polymer was extruded from the bottom of the reactor ina strand form into cooling water and cut with a strand cutter intochips. Table 1 shows the results.

[0069] The resultant chips were melted at 250° C. using an extrusionspinning machine equipped with a spinneret provided with 36 circularspinning holes having a hole diameter of 0.27 mm and spun at athroughput of 34 g/min and a takeoff speed of 2400 m/min. The resultingundrawn yarn was fed to a drawing treating machine equipped with aheating roller at 60° C. and a plate heater at 160° C. and subjected todrawing treatment at a draw ratio of 1.7 times to provide an 83 dtex/36filament drawn yarn. Table 2 shows the results.

Example 2

[0070] Procedures were carried out in the same manner as in Example 1,except that 0.0316 part by weight of manganese acetate tetrahydrate and0.0038 part by weight of cobalt acetate tetrahydrate were used incombination as a transesterification catalyst in Example 1. Tables 1 and2 show the results.

Example 3

[0071] Procedures were carried out in the same manner as in Example 1,except that the polymerizing reaction catalyst was changed from thetitanium tetrabutoxide and the catalyst prepared in Reference Example 1in an amount of 30 mmole % expressed in terms of titanium atom was usedin Example 1. Tables 1 and 2 show the results.

Example 4

[0072] Procedures were carried out in the same manner as in Example 1,except that the polymerizing reaction catalyst was changed from thetitanium tetrabutoxide and the catalyst prepared in Reference Example 2in an amount of 30 mmole % expressed in terms of titanium atom was usedin Example 1. Tables 1 and 2 show the results.

Example 5

[0073] Procedures were carried out in the same manner as in Example 1,except that the polymerizing reaction catalyst was changed from thetitanium tetrabutoxide and the catalyst prepared in Reference Example 3in an amount of 30 mmole % expressed in terms of titanium atom was usedin Example 1. Tables 1 and 2 show the results.

Example 6

[0074] Procedures were carried out in the same manner as in Example 1,except that 0.009 part by weight of trimethyl phosphate was added aftercompleting the transesterification in Example 1. Tables 1 and 2 show theresults.

Example 7

[0075] Procedures were carried out in the same manner as in Example 2,except that 0.009 part by weight of trimethyl phosphate was added aftercompleting the transesterification in Example 2. Tables 1 and 2 show theresults.

Example 8

[0076] The chips obtained by the procedures in Example 1 were melted at250° C. with an extrusion spinning machine equipped with a spinneretprovided with 36 circular spinning holes having a hole diameter of 0.27mm and spun at a throughput of 36 g/min and a takeoff speed of 3600m/min. The resulting undrawn yarn was fed to a drawing treating machineequipped with a heating roller at 60° C. and a plate heater at 160° C.and subjected to drawing treatment at a draw ratio of 1.2 times toafford an 83 dtex/36 filament drawn yarn. Tables 1 and 2 show theresults.

Example 9

[0077] The chips obtained by the procedures in Example 1 were meltedwith an extrusion spinning machine equipped with a spinneret providedwith 36 circular spinning holes having a hole diameter of 0.27 mm, spunat a throughput of 34 g/min and a takeoff speed of 2400 m/min and,without being wound once, fed to a drawing treating machine equippedwith a heating roller at 60° C. and a plate heater at 160° C. andsubjected to drawing treatment at a draw ratio of 1.7 times to providean 83 dtex/36 filament drawn yarn. Tables 1 and 2 show the results.

Example 10

[0078] A reactor equipped with a stirrer, a rectifying column and amethanol distilling off condenser was charged with 100 parts by weightof dimethyl terephthalate, 70.5 parts by weight of trimethylene glycoland 0.0526 part by weight of titanium tetrabutoxide as a catalyst andfurther 0.0126 part by weight of potassium acetate andtransesterification was carried out while slowly heating up the mixturefrom 140° C. and distilling off methanol produced as a result of thereaction. The internal temperature reached 210° C. after the passage of3 hours from the start of the reaction.

[0079] The resulting reaction product was then transferred to anotherreactor equipped with a stirrer and a glycol distilling off condenserand polymerizing reaction was carried out while slowly heating up thereaction product from 210° C. to 265° C. and reducing the pressure fromatmospheric pressure to a high vacuum of 70 Pa. The polymerizingreaction was finished when the intrinsic viscosity reached 0.75 whiletracing the melt viscosity of the reaction system.

[0080] The molten polymer was then extruded from the bottom of thereactor in a strand form into cooling water and cut with a strand cutterinto chips. Table 1 shows the results.

[0081] The obtained chips were melted at 250° C. with an extrusionspinning machine equipped with a spinneret provided with 36 circularspinning holes having a hole diameter of 0.27 mm at a throughput of 34g/min and a takeoff speed of 2400 m/min. The resulting undrawn yarn wasfed to a drawing treating machine equipped with a heating roller at 60°C. and a plate heater at 160° C. and subjected to drawing treatment at adraw ratio of 1.7 times to afford an 83 dtex/36 filament drawn yarn.Table 2 shows the results.

Example 11

[0082] Procedures were carried out in the same manner as in Example 10,except that the amount of the potassium acetate used was changed from0.0126 part by weight and 0.00758 part by weight of the potassiumacetate was used in Example 10. Tables 1 and 2 show the results.

Example 12

[0083] Procedures were carried out in the same manner as in Example 10,except that 0.0126 part by weight of potassium acetate was changed and0.0175 part by weight of sodium acetate trihydrate was used in Example10. Tables 1 and 2 show the results.

Example 13

[0084] Procedures were carried out in the same manner as in Example 10,except that 0.0126 part by weight of the potassium acetate was changedand 0.0085 part by weight of lithium acetate was used in Example 10.Tables 1 and 2 show the results.

Example 14

[0085] Procedures were carried out in the same manner as in Example 10,except that 0.0126 part by weight of potassium acetate was changed and0.0186 part by weight of rubidium acetate was used in Example 10. Tables1 and 2 show the results.

Example 15

[0086] Procedures were carried out in the same manner as in Example 10,except that 0.0126 part by weight of potassium acetate was changed and0.0227 part by weight of calcium acetate monohydrate was used in Example10. Tables 1 and 2 show the results.

Example 16

[0087] Procedures were carried out in the same manner as in Example 10,except that 0.0126 part by weight of potassium acetate was changed and0.0276 part by weight of magnesium acetate tetrahydrate was used inExample 10. Tables 1 and 2 show the results.

Example 17

[0088] Procedures were carried out in the same manner as in Example 10,except that the titanium tetrabutoxide was changed and the catalystprepared in Reference Example 1 in an amount of 30 mmole % expressed interms of titanium atom was used in Example 10. Tables 1 and 2 show theresults.

Example 18

[0089] Procedures were carried out in the same manner as in Example 10,except that the titanium tetrabutoxide was changed and the catalystprepared in Reference Example 2 in an amount of 30 mmole % expressed interms of titanium atom was used in Example 10. Tables 1 and 2 show theresults.

Example 19

[0090] Procedures were carried out in the same manner as in Example 10,except that 0.009 part by weight of trimethyl phosphate was added intothe reaction system just after completing the transesterification inExample 10. Tables 1 and 2 show the results.

Example 20

[0091] The chips obtained by procedures in Example 10 were melted at250° C. with an extrusion spinning machine equipped with a spinneretprovided with 36 circular spinning holes having a hole diameter of 0.27mm and spun at a throughput of 36 g/min and a takeoff speed of 3600m/min, and the resulting undrawn yarn was fed to a drawing treatingmachine equipped with a heating roller at 60° C. and a plate heater at160° C. and subjected to drawing treatment at a draw ratio of 1.7 timesto provide an 83 dtex/36 filament drawn yarn. Tables 1 and 2 show theresults.

Example 21

[0092] The chips obtained by procedures in Example 10 were melted at250° C. with an extrusion spinning machine equipped with a spinneretprovided with 36 circular spinning holes having a hole diameter of 0.27mm and spun at a throughput of 34 g/min and a takeoff speed of 2400m/min, and the resulting undrawn yarn, without being wound once, was fedto a drawing treating machine equipped with a heating roller at 60° C.and a plate heater at 160° C. and subjected to drawing treatment at adraw ratio of 1.7 times to afford an 83 dtex/36 filament drawn yarn.Tables 1 and 2 show the results.

Comparative Example 1

[0093] Procedures were carried out in the same manner as in Example 1,except that 0.0525 part by weight of the titanium tetrabutoxide was usedto carry out transesterification without using manganese acetatetetrahydrate and polymerizing reaction was then conducted withoutconducting further addition at all in Example 1. Table 1 shows theresults.

Comparative Example 2

[0094] Procedures were carried out in the same manner as in Example 1,except that the amount of the added manganese acetate tetrahydrate waschanged to 0.0885 part by weight in Example 1. Tables 1 and 2 show theresults.

Comparative Example 3

[0095] Procedures were carried out in the same manner as in Example 6,except that the amount of the added trimethyl phosphate was changed to0.027 part by weight in Example 6. Tables 1 and 2 show the results.

Comparative Example 4

[0096] Procedures were carried out in the same manner as in Example 10,except that the amount of the added potassium acetate was changed to0.0405 part by weight in Example 10. Tables 1 and 2 show the results.

Comparative Example 5

[0097] Procedures were carried out in the same manner as in Example 10,except that the amount of the added trimethyl phosphate was changed to0.027 part by weight in Example 10. Tables 1 and 2 show the results.TABLE 1 Polymer (2) P/M (8) (9) (1) mmole % (3) (4) (5) (6) Molar % by %by (10) Kind mmole % Kind (11) mmole % ppm ppm ppm Ratio (7) weightweight b value Ex. 1  Mn(OAc)₂.4H₂O 25 TBT 30 — — — 66 0.0 0.75 0.23 2.06.8 Ex. 2  Mn(OAc)₂.4H₂O 25 TBT 30 — — — 66 0.0 0.75 0.23 2.1 4.9Co(OAc)₂.4H₂O 3 Ex. 3  Mn(OAc)₂.4H₂O 25 TMT 30 — — — 66 0.0 0.75 0.252.1 6.5 Ex. 4  Mn(OAc)₂.4H₂O 25 TPO 30 — — — 66 0.5 0.75 0.26 2.0 6.0Ex. 5  Mn(OAc)₂.4H₂O 25 TPI 30 12.5 — — 66 0.5 0.75 0.24 2.1 6.2 Ex. 6 Mn(OAc)₂.4H₂O 25 TBT 30 12.5 — — 66 0.5 0.75 0.23 2.0 5.9 Ex. 7 Mn(OAc)₂.4H₂O 25 TBT 30 — — — 66 0.5 0.75 0.24 2.1 4.8 Co(OAc)₂.4H₂O 3Ex. 8  Mn(OAc)₂.4H₂O 25 TBT 30 — — — 66 0.0 0.75 0.23 2.0 6.8 Ex. 9 Mn(OAc)₂.4H₂O 25 TBT 30 — — — 66 0.0 0.75 0.23 2.0 6.8 Ex. 10 KOAc 25TBT 30 — 51 — — 0.0 0.75 0.21 2.1 6.6 Ex. 11 KOAc 15 TBT 30 — 31 — — 0.00.75 0.22 2.0 5.0 Ex. 12 Na(OAc)₂3H₂O 25 TBT 30 — 51 — — 0.0 0.75 0.232.1 6.0 Ex. 13 LiOAc 25 TBT 30 —  9 — — 0.0 0.75 0.22 1.9 5.5 Ex. 14RbOAc 25 TBT 30 — 111  — — 0.0 0.75 0.24 2.1 7.2 Ex. 15 Ca(OAc)₂.H₂O 25TBT 30 — — 52 — 0.0 0.75 0.23 2.2 6.0 Ex. 16 Mg(OAc)₂.4H₂O 25 TBT 30 — —32 — 0.0 0.75 0.21 2.0 5.6 Ex. 17 KOAc 25 TMT 30 — 51 — — 0.0 0.75 0.222.1 6.7 Ex. 18 KOAc 25 TPO 30 — 51 — — 0.0 0.75 0.20 2.1 6.8 Ex. 19 KOAc25 TBT 30 12.5 51 — — 0.5 0.75 0.21 1.9 5.5 Ex. 20 KOAc 25 TBT 30 — 51 —— 0.0 0.75 0.21 2.1 6.6 Ex. 21 KOAc 25 TBT 30 — 51 — — 0.0 0.75 0.21 2.16.6 (12) TBT 30 — — — — — — — 0.75 0.21 2.0 5.1 (13) Mn(OAc)₂.4H₂O 70TBT 30 — — — 185  0.0 0.75 0.25 2.1 10.5 (14) Mn(OAc)₂.4H₂O 25 TBT 3037.5 — — 66 1.5 0.75 0.22 2.0 5.5 (15) KOAc 70 TBT 30 — 142  — — 0.00.75 0.25 2.1 10.5 (16) KOAc 25 TBT 30 37.5 51 — — 1.5 0.75 0.22 2.0 5.5

[0098] TABLE 2 Drawn Yarn Light Resis- (1) (5) tance of Fabric m/ (2)(4) cN/ (6) Color b value min Times (3) dtex dtex % (7) (8) (9) Example1  2400 1.7 0.72 83 3.1 40 2.7 2.9 0.2 Example 2  2400 1.7 0.71 83 3.042 2.3 2.6 0.3 Example 3  2400 1.7 0.71 83 2.9 41 2.6 2.9 0.3 Example 4 2400 1.7 0.72 83 3.1 40 2.5 3.0 0.5 Example 5  2400 1.7 0.71 83 3.2 432.4 3.0 0.6 Example 6  2400 1.7 0.72 83 3.0 40 2.4 3.0 0.6 Example 7 2400 1.7 0.71 83 3.1 40 2.1 2.8 0.7 Example 8  3600 1.2 0.71 83 3.1 422.8 3.0 0.2 Example 9  2400 1.7 0.71 83 3.0 43 2.7 3.0 0.3 Example 102400 1.7 0.71 83 3.1 40 2.6 2.7 0.1 Example 11 2400 1.7 0.72 83 3.0 422.4 2.7 0.3 Example 12 2400 1.7 0.71 83 2.9 41 2.3 3.3 1.0 Example 132400 1.7 0.72 83 3.1 40 2.3 3.4 1.1 Example 14 2400 1.7 0.71 83 3.2 433.0 2.7 −0.3 Example 15 2400 1.7 0.72 83 3.0 40 2.0 3.0 1.0 Example 162400 1.7 0.71 83 3.1 40 2.1 3.3 1.2 Example 17 2400 1.7 0.72 83 3.0 412.7 2.8 0.1 Example 18 2400 1.7 0.72 83 3.0 39 2.5 2.8 0.3 Example 192400 1.7 0.71 83 3.1 40 2.3 2.6 0.3 Example 20 3600 1.2 0.71 83 3.1 422.7 2.8 0.1 Example 21 2400 1.7 0.71 83 3.0 43 2.7 2.9 0.2 (10) 2400 1.70.73 83 3.3 42 2.2 4.7 2.5 (11) 2400 1.7 0.71 83 2.9 39 5.6 5.8 0.2 (12)2400 1.7 0.72 83 3.1 41 2.5 4.7 2.2 (13) 2400 1.7 0.71 83 2.9 39 5.6 5.80.2 (14) 2400 1.7 0.72 83 3.1 41 2.5 4.7 2.2

Industrial Applicability

[0099] According to the present invention, there can be provided apolyester based on poly(trimethylene terephthalate) capable of improvinglight resistance of the polyester based on the poly(trimethyleneterephthalate) and suitable for producing formed products responsive towide demands because forming conditions such as yarn manufacturingconditions are not strictly limited. The industrial significance of thepresent invention is great.

1. A polyester based on poly(trimethylene terephthalate) consistingessentially of trimethylene terephthalate repeating units, comprising atleast one kind of compound selected from the group consisting of alkalimetal compounds, alkaline earth metal compounds and manganese compoundsin an amount of 10 to 150 ppm expressed in terms of the alkali metalelement in a molar ratio of the total amount of elements of thecontained alkali metal elements, alkaline earth metal elements andmanganese element to the amount of the contained phosphorus elementwithin the range of the following formula (I): 0≦P/M≦1  (I) wherein, Pis the molar amount the phosphorus element in the polyester; M is thetotal molar amount of the alkali metal elements, alkaline earth metalelements and manganese element
 2. The polyester according to claim 1,wherein the following respective requirements (a) to (d) aresimultaneously satisfied. (a) the intrinsic viscosity is within therange of 0.5 to 1.6, (b) the content of dipropylene glycol is within therange of 0.1 to 2.0% by weight based on the total weight of thepolyester, (c) the content of a cyclic dimer is within the range of 0.01to 5% by weight based on the total weight of the polyester and (d) thecolor b value is within the range of −5 to
 10. 3. The polyesteraccording to claim 1, wherein the alkali metal compounds are compoundsselected from the group consisting of lithium compounds, sodiumcompounds, potassium compounds and rubidium compounds.
 4. The polyesteraccording to claim 1, wherein the alkaline earth metal compounds aremagnesium compounds and/or calcium compounds.
 5. The polyester accordingto claim 1, wherein the manganese compounds are compounds selected fromthe group consisting of manganese acetate, manganese benzoate andmanganese chloride.
 6. A method for producing a polyester based onpoly(trimethylene terephthalate) comprising using a titanium compound asa polymerization catalyst when the polyester according to claim 1 isproduced.
 7. The method for production according to claim 6, wherein thetitanium compound is a titanium tetraalkoxide.
 8. The method forproduction according to claim 6, wherein the titanium compound is areaction product of at least one compound selected from the groupconsisting of phthalic acid, trimellitic acid, hemimellitic acid andpyromellitic acid or anhydrides thereof with a titanium tetraalkoxide.9. The method for production according to claim 6, wherein the titaniumcompound is a reaction product of a titanium tetraalkoxide with aphosphonic acid compound.
 10. The method for production according toclaim 6, wherein the titanium compound is a reaction product of atitanium tetraalkoxide with a phosphinic acid compound.
 11. The methodfor production according to claim 6, wherein the titanium compound is areaction product of a titanium tetraalkoxide with a phosphate compound.12. The method for production according to claim 6, wherein the titaniumcompound is a reaction product of a reaction product between at leastone compound selected from the group consisting of phthalic acid,trimellitic acid, hemimellitic acid and pyromellitic acid or anhdyridesthereof and a titanium tetraalkoxide with a phosphonic acid compound.13. The method for production according to claim 6, wherein the titaniumcompound is a reaction product of a reaction product between at leastone compound selected from the group consisting of phthalic acid,trimellitic acid, hemimellitic acid and pyromellitic acid or anhydridesthereof and a titanium tetraalkoxide with a phosphinic acid compound.14. The method for production according to claim 6, wherein the titaniumcompound is a reaction product of a reaction product between at leastone compound selected from the group consisting of phthalic acid,trimellitic acid, hemimellitic acid and pyromellitic acid or anhydridesthereof and a titanium tetraalkoxide with a phosphate compound. 15.Polyester fibers based on poly(trimethylene terephthalate) which areobtained by melt spinning the polyester based on the poly(trimethyleneterephthalate) according to claim 1 at a melting temperature of 238 to275° C. and a spinning speed of 400 to 5000 m/min.
 16. A polyester drawnyarn based on the poly(trimethylene terephthalate) obtained afterwinding the fibers according to claim 15 once or without winding thefibers once and continuously subjecting the fibers to drawing treatment.17. A fabric which is composed of a polyester comprising the polyesterfibers based on the poly(trimethylene terephthalate) according to claim15 and has an increase in color b value of 2 or below after irradiationat 60° C. for 80 hours using a sunshine weatherometer.
 18. A fabricwhich is composed of a polyester comprising the polyester drawn yarnbased on the poly(trmethylene terephthalate) according to claim 15 andhas an increase in color b value of 2 or below after irradiation at 60°C. for 80 hours using a sunshine weatherometer.